Use as catalyst in the hydroformylation of olefinic feedstock to higher aldehydes and higher alcohols

ABSTRACT

A method for producing a potassium paradiphenyl phosphino sulfonate ligand which comprises reacting potassium diphenyl phosphide with a lithium salt of para-chloro benzenesulfonic acid in the presence of tetrahydrofuran at elevated temperatures.

This is a division of application Ser. No. 006,910, filed Jan. 21, 1993.

The present invention relates generally to a novel ligand that is usefulfor hydroformylation of higher α-olefins in an aqueous emulsion. Theligand is a potassium para-diphenyl phosphino benzene sulfonate which issynthesized rapidly and in extremely high yields.

BACKGROUND OF THE INVENTION

Hydroformylation reactions involve the preparation of oxygenated organiccompounds by the reaction of carbon monoxide and hydrogen (i.e.,synthesis gas) with carbon compounds containing olefinic unsaturation.The reaction is typically performed in the presence of a carbonylationcatalyst and results in the formation of compounds, for example,aldehydes, which have one or more carbon atoms in their molecularstructure than the starting olefinic feedstock. By way of example,higher alcohols may be produced by hydroformylation of commercial C₆-C₁₂ olefin fractions to an aldehyde-containing oxonation product, whichon hydrogenation yields the corresponding C₇ -C₁₃ saturated alcohols.The crude product of the hydroformylation reaction will containcatalyst, aldehydes, alcohols, unreacted olefin feed, synthesis gas andby-products.

A variety of transition metals catalyze the hydroformylation reaction,but only cobalt and rhodium carbonyl complexes are used in commercialplants. The reaction is highly exothermic, i.e., the heat release isapproximately ca 125 kJ/mol (30 kcal/mol). The position of the formylgroup in the aldehyde product depends upon the olefin type, thecatalyst, the solvent, and the reaction conditions. Reaction conditionshave some effect and, with an unmodified cobalt catalyst, the yield ofstraight chain product from a linear olefin is favored by higher carbonmonoxide partial pressure. In the hydroformylation of terminal olefinichydrocarbons, the use of a catalyst containing selected complexingligands, e.g., tertiary phosphines, results in the predominant formationof the normal isomer.

In commercial operation, the aldehyde product is typically used as anintermediate which is converted hydrogenation to an alcohol or byaldolization and hydrogenation to a higher alcohol. Thealdol-hydrogenation route is used primarily for the manufacture of2-ethylhexanol from propylene that is converted to n-butyraidehyde.

Much research in the past 25 years has been directed to improvingreaction selectivity to the linear product. Introduction of anorganophospnine ligand to form a complex, e.g., Co(CO)₆ [P(n-C₄ H₉)₃ ]2,significantly improves the selectivity to the straight chain alcohol.

Recent developments of low pressure rhodium catalyst systems have beenthe subject of a considerable body of patent art and literature, andrhodium-triphenyl phosphine systems have been widely, and successfully,used commercially for the hydroformylation of propylene feedstocks toproduce butyraldehyde.

Homogeneous catalysts formed from ligated metal atoms can perform veryselective chemistries with high turnover rates. For example, rhodiumcomplexes containing phosphine ligands have ideal properties ascatalysts in the hydroformylation process used in making long chainaldehydes because of their propensity to form the linear rather thanbranched isomers. The linear aldehydes which can be formed with rhodiumcatalyst complexes are needed for formulating biodegradable detergents,plasticizers, specialty polymers, etc. Homogeneous rhodium catalystcomplexes have a unique role in this chemistry in that they can take alinear terminal olefin and convert it into a predominantly linearaldehyde.

A typical homogeneous rhodium complex catalyst is formed withtriphenylphosphine ligands in the presence of carbon monoxide andhydrogen. The rhodium bonds to the triphenylphosphine ligand through aphosphorous atom. A large number of complexes are formed betweenrhodium, triphenylphosphine, hydrogen, and carbon monoxide, because theyform loosely bound molecular species which are involved in multipleequilibria as they dissociate and recombine with ligands in solution.One of the complexes can be a very active catalyst for thehydroformylation reaction which converts linear olefins into the nexthigher carbon number linear aldehydes by the addition of carbon monoxideand hydrogen. In addition, the catalyst converts some of the productaldehyde to dimer and trimer condensation products. The isomerizationactivity of the catalyst in extremely undesirable in applicationsdesigned to produce long chain linear aldehydes. Linear aldehydescontaining between 12 to 15 carbon are readily hydrogenated to linearalcohols which are premium products for formulating biodegradable liquiddetergents.

Others have synthesized high molecular weight phosphine ligands for useas homogeneous catalysts. High molecular weight polymeric phosphineligands are synthesized by reacting polyvinylchloride, polychloropreneor brominated polystyrene with lithium diphenylphosphide at 20° C. to25° C. These homogeneous catalysts containing bulky ligands are thoughtto be more easily separated from the reaction products byultrafiltration. See Imyanitov et al., All-Union Scientific ResearchInstitute of Petrochemical Processes, Neftekhimiya, 32, No. 3:200-7(May-June 1992).

One conventional rhodium ligand used in the hydroformylation of higherα-olefins, such as 1-dodecene in an aqueous emulsion catalytic process,is sodium p-diphenyl phosphino benzoate, i.e., Ph₂ P(pC_(C) ₆ H₄ COO₃Na). As discussed in Great Britain Patent Application No. 2,085,874,filed on Aug. 21, 1981, this rhodium ligand complex is active at lowtemperature and pressure, and gives a high selectivity to the normalisomer.

Still others have synthesized a rhodium ligand complex using a Ph₂P(m-C₆ H₄ SO₃ Na) ligand as shown in Ahrland et al., "The relativeAffinities of Co-ordinating Atoms for Silver Ion. Part II.¹ Nitrogen,Phosphorus, and Arsenic.^(2:), Chemical Society, 1958, pp. 276-288. ThePh₂ P(m-C₆ H₄ SO₃ Na) ligand was synthesized by slowly adding 10 gramsof triphenylphosphine, with cooling, to a mixture of 20% SO₃ -H₂ SO₄ (19c.c.) and 65% SO₃ -H₂ SO₄ (1 c.c.). The phosphine dissolved and thesolution was heated on a water bath. The solution was tested atintervals by adding one drop to water (2-3 c.c.) until a test drop gavea clear or only slightly cloudy aqueous solution (1-2 hours depending onthe acid strength). The acid solution was cooled, poured cautiously intowater (200 c.c.) and neutralized with saturated sodium hydroxidesolution. The product separated as fine, white shining leaves.

As demonstrated in comparative Example 3, the sodium m-diphenylphosphino benzene sulfonate (i.e., Ph₂ P(m-C₆ H₄ SO₃ Na)) ligand whichwas synthesized by direct sulfonation of triphenyl phosphine resulted invery low rates of reaction in the hydroformylation of 1-decene and a lowselectivity to the desired normal isomer compared to the correspondingpara substituted carboxylic or sulfonic acid ligands.

Sodium p-diphenyl phosphino sulfonate, i.e., Ph₂ P(p-C₆ H₄ SO₃ Na), wasfirst synthesized by H. Schindlbauer (see H. Schindlbauer, Monatsh Chem,96 (6), 1965, pp. 2051) from potassium diphenyl phosphide and p-chlorosodium benzoate by boiling at 67° C. in tetrahydrofuran (THF) for 24hours. This article describes the formation of a by-product, p-diphenylphosphino benzene, i.e., Ph₂ P(p-C₆ H₄ PPh₂), resulting fromdisplacement of the sulfonic group by the diphenyl phosphino group, butgives no yield for the sulfonic salt, i.e., Ph₂ P(p-C₆ H₄ SO₃ Na), whichwas identified by elemental analysis for phosphorus and sulfur but couldnot be recrystallized due to poor solubility

The present inventors have discovered that by using a lithium salt ofthe p-chloro benzene sulfonic acid, i.e., Cl(p-C₆ H₄ SO₃ Li) in areaction with potassium diphenyl phosphide enables the isolation andpurification of the product compound in high yield and purity. Since thelithium salt is more soluble then the corresponding sodium salt in THF,the reaction proceeds in 0.5 hours in boiling THF which is substantiallyfaster than the formation of Ph₂ P(pC_(C) ₆ H₄ SO₃ Na) from Cl(p-C₆ H₄SO₃ Na). Moreover, the potassium salt (Ph₂ P(p-C₆ H₄ SO₃ K)) of theligand as a result of a lithium/potassium salt exchange is obtained inan approximate yield of 50%. Also, the potassium salt of the ligand wasfound to be less soluble in organic solvents then the conventionalsodium salts, such that it was able to be recrystallized from EtOH. Thepotassium salt was identified by elemental analysis, IR and P31 NMR.

Conventional hydroformylation reactions take place in an aqueousemulsion, such as that described in Great Britain Application No.2,085,874, filed Aug. 21, 1981, in which the aqueous phase consists of a1N NaHCO₃ solution, thus generating an excess of sodium cations.Therefore, since the potassium ligand salt is soluble in water it isconsequently exchanged "in situ" to the sodium salt. As such, when thePh₂ P(p-C₆ H₄ SO₃ K) ligand complexed catalyst is used to hydroformylate1-decene it exhibits comparable rates of conversion to both Ph₂ P(p-C₆H₄ SO₃ Na) and Ph₂ P(p-C₆ H₄ COO₃ Na) ligands, and substantially higherrates of conversion than Ph₂ P(m-C₆ H₄ SO₃ Na).

The present invention also provides many additional advantages whichshall become apparent as described below.

SUMMARY OF THE INVENTION

A method for producing a potassium para-diphenyl phosphino sulfonateligand by reacting potassium diphenyl phosphide with a lithium salt ofpara-chloro benzenesulfonic acid in the presence of at least onecompound selected from the group consisting of: tetrahydrofuran,1,4-dioxane and 2-ethoxyethyl ether, at a temperature in the rangebetween about 65° to about 100° C. for between about 0.25 to 1 hours.

This group VIII noble metal-ligand complex catalyst is preferably usedin hydroformylation of olefins in the presence of synthesis gas. Thepresent invention also encompasses a method for producing higheraldehydes and higher alcohols by hydroformylating an olefinic feedstockwith synthesis gas in the presence of this novel Group VIII noblemetal-ligand complex catalyst which forms a crude reaction product of anolefin feed, a hydroformylation reaction product and the Group VIIInoble metal-ligand complex catalyst.

Other and further objects, advantages and features of the presentinvention will be understood by reference to the followingspecification.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hydroformylation is a process of converting olefins to a product of oneor more additional carbon numbers by the addition of carbon monoxide andhydrogen to the double bond(s) of the olefin in the presence of acatalyst at elevated temperatures and pressures. A typicalhydroformylation process is demonstrated below: ##STR1##

At a temperature of 100° C. and a pressure of 12.75 kg (150 lbs.) thenormal to iso ratio using rhodium as the catalyst may be below 1 or evenas high as 100, depending on the ligand, ratio of ligand to rhodium,etc. Homogeneous rhodium-ligand complex catalysts are able to take alinear terminal olefin and convert it into a predominantly linearaldehyde.

A potassium para-diphenyl phosphino sulfonate ligand is formed byreacting potassium diphenyl phosphide with a lithium salt of para-chlorobenzenesulfonic acid in the presence of at least one compound selectedfrom the group consisting of: tetrahydrofuran, 1,4-dioxane and2-ethoxyethyl ether, at a temperature in the range between about 65° toabout 100° C. for between about 0.25 to 1 hours.

The potassium diphenyl phosphide is produced from the reaction productof diphenyl chloropnosphine and potassium in the presence of at leastone compound selected from the group consisting of: tetrahydrofuran,1,4-dioxane and 2-ethoxyethyl ether, at a temperature in the rangebetween about 65° to about 100° C. for between about 0.25 to 1 hours.

The potassium para-diphenyl phosphino sulfonate ligand (Ph₂ P(p-C₆ H₄SO₃ K)) according to the present invention is preferably synthesizedfrom potassium diphenyl phosphide (Ph₂ PK) and the lithium salt ofp-chloro benzenesulfonic acid (Cl(p-C₆ H₄ SO₃ Li)) by boiling intetrahydrofuran (THF) for approximately 0.5 hours as shown in the belowequations: ##STR2##

Due to Li/K salt exchange, the yield of potassium p-diphenyl phosphinosulfonate during the synthesis process is approximately 50%. Thepotassium ligand salt is soluble in water. The hydroformylation takesplace in an aqueous emulsion in which the aqueous phase consists of a 1NNaHCO₃ solution, thus giving an excess of sodium cations. The potassiumsalt of the ligand is consequently exchanged "in situ" with the sodiumsalt. The aqueous phase contains sodium bicarbonate and a surfactantsuch as lauric acid in addition to the ligand-sodium salt.

This Group VIII metal-ligand complex catalyst is particularly useful inproducing higher aldehydes and higher alcohols which compriseshydroformylating an olefinic feedstock with synthesis gas in thepresence of the Group VIII noble metal-ligand complex catalyst to form acrude reaction product comprised of an olefin feed, a hydroformylationreaction product and the Group VIII noble metal-ligand complex catalyst.

In the below examples, the organic phase solution contains the olefin,e.g., 1-decene, the Rh catalyst precursor, a co-solvent such as i-PrOHand, as an internal standard for gas chromatographic (GC) analysis, anon-reactive compound such as hexadecane. The two solutions areintroduced in an autoclave and pressurized to 10 psig at roomtemperature with a mixture of carbon monoxide to hydrogen of 1:1. Theautoclave is heated at 80° C. while the pressure is maintained at 150psig. The reaction is monitored by periodic GC analysis of samples takenfrom the organic phase.

EXAMPLE 1 (Synthesis of Ph₂ P(p-C₆ H₄ SO₃ K))

28.30 grams of diphenyl chlorophosphine were added to 10 grams of afinely dispersed suspension of potassium, the suspension of potassiumwas obtained under vigorous stirring in 400 ml of THF at 67° C. in anitrogen atmosphere, dropwise at a sufficient rate to maintain constantreflux without external heating. As the reaction proceeded, thepotassium disappeared and Ph₂ PK appeared as an intense purple compound.After the diphenyl chlorophosphine had been completely added to thesuspension of potassium, the solution was cooled to 45°-50° C.Thereafter, 25.47 grams of a well dried p-chloro lithium sulfonate wasadded to the Ph₂ PK under a nitrogen blanket. This solution was thenheated to reflux with stirring. The change in color from purple to lightbrown, which took place within 0.5 hours, indicated the disappearance ofthe potassium diphenyl phosphide. The solution was cooled, whilestirring, to room temperature, and 250 cc of water was added. Themixture was extracted times with 100 cc of ether. The aqueous solutionwas concentrated on the rotary evaporator at 50°-60° C. to approximatelyhalf the original volume. A white precipitate appeared. The solution wascooled, filtered, washed with cold ethanol and dried under nitrogen togive 25 grams of product and a yield of 49% of Ph₂ P(p-C₆ H₄ SO₃ K).

The compound analysis for Ph₂ P(p-C₆ H₄ SO₃ K) having a molecular weightof 380 calculated for C=56.84, H=3.69, P=8.16, O=12/63, K=10.26 andS=8.42% found: C=56.68, H=3.93, P=7.51, K=10.36, S=8.01%. P31 NMRdetected one peak of -3.6396 ppm (with 85% H₃ PO₄ ext. reference). TheIR=1210-1050, CM- for SO₃ -, 827 CM-1 1,4 disubst. benzene, 1479,750,697 CM-1 for (C₆ H₅)₂ P.

The lithium p-chloro benzene sulfonate was obtained from thecorresponding acid by exchange with LiOH in aqueous ethanol,neutralization of the excess Li0H with carbon dioxide, and dryingASTM/Toluene followed by high vacuum.

EXAMPLE 2 (Sodium p-Diphenyl Phosphino Benzoate Ligand)

2 grams of lauric acid, as surfactant, were added to an aqueous solutionof which consisted of sodium p-diphenyl phosphino benzoate (Ph₂ P(p-C₆H₄ COO₃ Na)), dissolved at approximately 70° C. with stirring undernitrogen in 70 grams of 1N NaHCO₃ solution. The resulting clear solutionwas then introduced through a Hoke bomb to a 1 liter autoclave. To thissolution, a mixture which consisted of 179.23 gms of 1-decene, 9.93grams of hexadecane as an internal standard, 1.24E-01 grams of rhodiumacetate dimer (i.e., RhII₂ (OOCCH₃)₄ dimer) and 10 grams of i-PrOH ascosolvent were introduced through the Hoke bomb under a carbonmonoxide/hydrogen pressure.

The autoclave was pressurized with a mixture of CO/H₂ in a ratio of 1:1and at a pressure of 100 psig at room temperature. The contents werethen heated to 80° C. while the pressure was maintained at 150 psig. Thereaction was monitored by periodic GC analysis of the organic layer. Thedata is set forth below in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                       Mole %                                                                     Time                                                                             Conversion                                                                           Selectivity                                                                          Ratio                                        Run No.                                                                            Ligand Type                                                                              Hour                                                                             of 1-Decene                                                                          to Aldehyde                                                                          N/I TON                                      __________________________________________________________________________    1    Ph.sub.2 P(p-C.sub.6 H.sub.4 SO.sub.3 Na)                                                0.50                                                                             5.26   76.00  15.87                                                                             239                                      2    Ph.sub.2 P(p-C.sub.6 H.sub.4 SO.sub.3 Na)                                                1.00                                                                             13.59  86.56  15.94                                                                             345                                      3    Ph.sub.2 P(p-C.sub.6 H.sub.4 SO.sub.3 Na)                                                2.00                                                                             21.50  88.83  15.69                                                                             172                                      4    Ph.sub.2 P(p-C.sub.6 H.sub.4 SO.sub.3 Na)                                                3.00                                                                             31.47  91.24  15.14                                                                             213                                      5    Ph.sub.2 P(p-C.sub.6 H.sub.4 SO.sub.3 Na)                                                4.00                                                                             42.25  91.42  14.95                                                                             243                                      __________________________________________________________________________     TON = Moles Conv. (Sel to Ald./100)/g.at. Rh Hr.                         

EXAMPLE 3 (Sodium m-Diphenyl Phosphino Benzene Sulfonate Ligand)

2 grams of lauric acid, as surfactant, were added to an aqueous solutionof which consisted of sodium m-diphenyl phosphino benzene sulfonate (Ph₂P(m-C₆ H₄ SO₃ Na)), dissolved at approximately 70° C. with stirringunder nitrogen in 70 grams of 1N NaHCO₃ solution. The resulting clearsolution was then introduced through a Hoke bomb to a 1 liter autoclave.To this solution, a mixture which consisted of 181.56 grams of 1-decene,12.20 grams of hexadecane as an internal standard, 1.22E-01 grams ofRhII₂ (OOCCH₃)₄ dimer and 1.0 grams of i-PrOH as co-solvent wereintroduced through the Hoke bomb under a carbon monoxide/hydrogenpressure.

The autoclave was pressurized with a mixture of CO/H₂ in a ratio of 1:1and at a pressure of 100 psig at room temperature. The contents werethen heated to 80° C. while the pressure was maintained at 150 psig. Thereaction was monitored by periodic GC analysis of the organic layer. Thedata is set forth below in Table 2.

                                      TABLE 2                                     __________________________________________________________________________                       Mole %                                                                     Time                                                                             Conversion                                                                           Selectivity                                                                          Ratio                                        Run No.                                                                            Ligand Type                                                                              Hour                                                                             of 1-Decene                                                                          to Aldehyde                                                                          N/I TON                                      __________________________________________________________________________    1    Ph.sub.2 P(m-C.sub.6 H.sub.4 SO.sub.3 Na)                                                0.50                                                                             0.55   34.18  13.35                                                                             25                                       2    Ph.sub.2 P(m-C.sub.6 H.sub.4 SO.sub.3 Na)                                                1.00                                                                             0.57   33.12  9.85                                                                              13                                       3    Ph.sub.2 P(m-C.sub.6 H.sub.4 SO.sub.3 Na)                                                2.00                                                                             0.78   41.04  6.82                                                                               9                                       4    Ph.sub.2 P(m-C.sub.6 H.sub.4 SO.sub.3 Na)                                                18.00                                                                            3.27   83.25  6.39                                                                               4                                       __________________________________________________________________________

EXAMPLE 4 (Potassium p-Diphenyl Phosphino Benzene Sulfonate Ligand )

2 grams of lauric acid, as surfactant, were added to an aqueous solutionof which consisted of sodium p-diphenyl phosphino benzene sulfonate (Ph₂P(p-C₆ H₄ SO₃ K)), dissolved at approximately 70° C. with stirring undernitrogen in 70.84 grams of 1N NaHCO₃ solution. The resulting clearsolution was then introduced through a Hoke bomb to a 1 liter autoclave.To this solution, a mixture which consisted of 180.13 grams of 1-decene,10.34 grams of hexadecane as an internal standard, 1.44E-01 grams ofrhodium carbonyl acetyl acetonate (RhI(CO)₂ (C₅ H₇ O₂)) and 15 grams ofi-PrOH as co-solvent were introduced through the Hoke bomb under acarbon monoxide/hydrogen pressure.

The autoclave was pressurized with a mixture of CO/H2 in a ratio of 1:1and at a pressure of 100 psig at room temperature. The contents werethen heated to 80° C. while the pressure was maintained at 150 psig. Thereaction was monitored by periodic GC analysis of the organic layer. Thedata is set forth below in Table 3.

                                      TABLE 3                                     __________________________________________________________________________                      Mole %                                                                     Time                                                                             Conversion                                                                           Selectivity Ratio                                    Run No.                                                                            Ligand Type                                                                             Hour                                                                             of 1-Decene                                                                          to Aldehyde                                                                            N/I TON                                     __________________________________________________________________________    1    Ph.sub.2 P(p-C.sub.6 H.sub.4 SO.sub.3 K)                                                0.50                                                                             11.30  94.50    14.86                                                                             505                                     2    Ph.sub.2 P(p-C.sub.6 H.sub.4 SO.sub.3 K)                                                1.00                                                                             16.62  94.52    13.56                                                                             238                                     3    Ph.sub.2 P(p-C.sub.6 H.sub.4 SO.sub.3 K)                                                2.50                                                                             33.81  94.20    13.23                                                                             257                                     4    Ph.sub.2 P(p-C.sub.6 H.sub.4 SO.sub.3 K)                                                4.00                                                                             49.00  94.47    13.06                                                                             225                                     5    Ph.sub.2 P(p-C.sub.6 H.sub.4 SO.sub.3 K)                                                10.00                                                                            85.87  95.53    12.62                                                                             135                                     __________________________________________________________________________

When Tables 1, 2 and 3 are compared it becomes abundantly clear that therhodium hydroformylation of 1-decene with potassium p-diphenyl phosphinebenzene sulfonate (Ph₂ P(p-C₆ H₄ SO₃ K)) exhibited slightly higher ratesof conversion as compared to Ph₂ P(p-C₆ H₄ COO₃ Na). For example, after4 hours of reaction in the hydroformylation reactor the rhodium catalystof the present invention having a Ph₂ P(p-C₆ H₄ SO₃ K) ligand convertedapproximately 49.00 mole percent of 1-decene to aldhyde, whereas theconventional rhodium catalyst with a Ph₂ P(p-C₆ H₄ COO₃ Na) ligand onlyconverted approximately 42.25 mole percent. Furthermore, the Ph₂ P(p-C₆H₄ SO₃ K) converted more than twenty times as much as the rhodiumcatalyst with a Ph₂ P(m-C₆ H₄ SO₃ Na) ligand. The rhodium catalyst witha Ph₂ P(p-C₆ H₄ SO₃ K) ligand also exhibited an increased selectivity toaldehydes verses the Ph₂ P(p-C₆ H₄ COO₃ Na) and Ph₂ P(m-C₆ H₄ SO₃ Na)ligands.

While we have shown and described several embodiments in accordance withour invention, it is to be clearly understood that the same aresusceptible to numerous changes apparent to one skilled in the art.Therefore, we do not wish to be limited to the details shown anddescribed but intend to show all changes and modifications which comewithin the scope of the appended claims.

What is claimed is:
 1. A method for producing higher aldehydes andhigher alcohols which comprises hydroformylating an olefinic feedstockat elevated temperatures with synthesis gas in the presence of a GroupVIII noble metal-ligand complex catalyst to form a crude reactionproduct comprised of an olefin feed, a hydroformylation reaction productand a Group VIII noble metal-ligand complex catalyst, wherein said GroupVIII noble metal-ligand complex catalyst is a Group VIII noble metalcomplexed with a potassium para-diphenyl phosphino sulfonate ligand. 2.The method according to claim 1 wherein said potassium para-diphenylphosphino sulfonate ligand is the reaction product of potassium diphenylphosphide and a lithium salt of para-chloro benzenesulfonic acid.
 3. Themethod according to claim 2 wherein said potassium diphenyl phosphideand lithium salt of parachloro benzenesulfonic acid are reacted in thepresence of at least one compound selected from the group consisting of:tetrahydrofuran, 1,4-dioxane and 2ethoxyethyl ether.
 4. The methodaccording to claim 2 wherein said potassium diphenyl phosphide andlithium salt of parachloro benzenesulfonic acid are heated at atemperature in the range between about 65° to about 100° C.
 5. Themethod according to claim 2 wherein said potassium diphenyl phosphideand lithium salt of parachloro benzenesulfonic acid are reacted forbetween about 0.25 to about 100 hours.
 6. The method according to claim2 wherein said potassium diphenyl phosphide is produced from thereaction product of diphenyl chlorophosphine and potassium.
 7. Themethod according to claim 6 wherein said diphenyl chlorophosphine andpotassium are reacted in the presence of at least one compound selectedfrom the group consisting of: tetrahydrofuran, 1,4-dioxane and2-ethoxyethyl ether.
 8. The method according to claim 6 wherein saiddiphenyl chlorophosphine and potassium are reacted at a temperature inthe range between about 65° to about 100° C.
 9. The method according toclaim 1 wherein said olefinic feedstock is a C₆ to C₁₂ olefin.
 10. Themethod according to claim 9 wherein said olefinic feedstock is 1-decene.11. The method according to claim 1 wherein said olefinic feedstock isreacted with synthesis gas in the presence of a Group VIII noblemetal-ligand complex catalyst at a temperature of about 80° C.